Organo-phosphorus compounds containing perfluoroalkyl radicals and aziridine radicals

ABSTRACT

Perfluoroalkyl iodide monomer and telomer ester adducts of diethyl vinylphosphonate were prepared by free radical addition. Iodine of these adducts was replaced by hydrogen, and derivatives of the reduced phosphonate adducts were prepared, which include phosphonic acids, acid chlorides, and aziridinyl phosphine oxides. The aziridinyl phosphine oxides are used to impart oil and water repellency to cellulosic textiles. The other derivatives are useful as chemical intermediates as well as potential foaming agents.

United States Patent n 1 [in 3,910,886

Chance et al. Oct. 7, 1975 [54] ORGANO-PHOSPHORUS COMPOUNDS 3,585,1456/l97l Fethke 260/955 S CQ E E FOREIGN PATENTS OR APPLICATIONS RA CA A ARID E RADICALS l 454,535 8/1966 France .w 260/955 [75] Inventors: LeonH. Chance; Jerry P. Moreau,

both of New Orleans, La. OTHER PUBLICATIONS [73] Assignee: The UnitedStates of America as Brace Chem" VOL 3 l97 320l ([96! represented by theSecretary of I Agriculture, Washington DC. Primary [:xammer-Alton D.Rollins Attorney. Agent, or FirrnM. Howard Silverstein; Max June 9,Hens'gy [21] Appl. No.: 151,507

Related [1.8. Application Data [57] ABSTRACT [62] Division of Sen N0 843200 July 18 1969 Pat NO Perfluoroalkyl iodide monomer and telomer esterad- 3639144 i I I ducts of diethyl vinylphosphonate were prepared byfree radical addition iodine of these adducts was re- [52 vs. C! 260/239EP Placed by hydmgem and derivatives of the reduced 51 m. cm C07F 9/56phosphhhate adducls were Prepared which include {58] Field of Search260/239 EP, 955 phhsphohic acids acid chlorideh and alhidihyl P phineoxides. The aziridinyl phosphine oxides are used {56] References Citedto impart oil and water repellency to cellulosic tex- UNITED STATESPATENTS tiles. The other derivatives are useful as chemical in- Itermediates as well as potential foaming agents. 2,559.754 7/[95]Bittles et a] .6 260/955 2,899,454 8/[959 McBee et al 260/955 1 Claim,N0 Drawings ORGANO-Pl-IOSPHORUS COMPOUNDS CONTAINING PERFLUOROALKYLRADICALS AND AZIRIDINE RADICALS A non-exclusive, irrevocable,royalty-free license in the invention herein described, throughout theworld for all purposes of the United States Government, with the powerto grant sublicenses for such purposes, is hereby granted to theGovernment of the United States of America.

This application is a division of application bearing Ser. No. 843,200,filed July 18, I969, now U.S. Pat. No. 3,639,144.

This invention relates to perfluoroalkyl adducts of diethylvinylphosphonate, to derivatives thereof, to the preparation thereof,and to processes for imparting improved properties to cellulosictextiles by treating said textiles with certain of the perfluoroalkylphosphorus derivatives of this invention. More specifically, thisinvention relates to the preparation of perfluoroalkyl phosphonateesters and to the corresponding acids, acid chlorides, and aziridinylderivatives, useful in oil and water repellent finishes for textiles andalso useful as chemical intermediates and potential foaming agents.

DEFINITIONS l. Te/omens are polymers of low molecular weight such as areencountered, for example, in the freeradical addition of an addendum XYto ethylene, which may be represented as where n is small; the processis known as telomerization. Kingzetts Chemical Encyclopaedia, 9th Ed.

2. Telumerizurion does not differ essentially from other polymerizationcatalyzed by free radicals. It arises merely because enough of asufficiently reactive compound is present to act as a chain transferreagent, but the concentration and reactivity are not high enough togive rise chiefly to l,2, addition." Carl R. Noller's Chemistry ofOrganic Compounds" The main object of the instant invention is toprovide new phosphonic compounds containing a perfluoroalkyl radicalconnected to the phosphorus atom by an ethylene (-CH CH linkage.

A second object of the instant invention is to provide methods ofpreparing new perfluoroalkyl phosphonic compounds.

A third object of the instant invention is to provide a process forimparting to cotton and other cellulosic materials both oil and waterrepellency using some of the new compounds of the instant invention.

A fourth object of the invention is to provide a process for impartingto cotton and other cellulosic textiles resistance to soiling andstaining.

Searching the prior art we find that a dialkyl phosphonate reacts withtetrafluoroethylene in a pressure vessel using a free radical initiatorto produce products of the general formula H(CF CH ),,PO(OR) [Neal D.Brace, J. Org. Chem. 26, 3197 I96] These products have a terminalhydrogen atom on the perfluoro group, and consequently are not aseffective in producing oil and water repellency as similar products inwhich the terminal hydrogen is replaced by a fluorine atom.

One improvement which is a facet of the present invention over the priorart is this. We have found that compounds of the present inventionimpart excellent oil repellency and moderate water repellency tocellulosic materials because the perfluoro group has a terminal CF groupinstead of a terminal HCF group.

In the course of investigation we have found that compounds of thegeneral formula graphic formula (A) to produce products represented bythe following equations:

Reducing C F n (H -CH H agent I acid it-C H hydrolysis l aziridine u aunwhere n is an integer from I to l0, and v is an integer from I to 3.

In accordance with the present invention the reaction of the dialkylvinylphosphonate with the perfluoroalkyl iodide is carried out byheating in the presence of a select catalyst. Typical catalysts suitablefor the reaction are organic peroxides, such as ditertbutyl peroxide orazobisnitriles such as azobis(isobutyronitrile). Two main products areobtained from this type reaction and include the monomericperfluoroalkyl iodide adduct and a telomer in which the dialkylphosphonate moiety is dimeric. A mixture of unidentified highermolecular weight telomers are also obtained. Typical examples arerepresented by the reaction of diethyl vinylphosphonate andperfluoroheptyl iodide to give a monomeric phosphonate ester of theformula and a telomer ester of the formula Also in accordance with thepresent invention the iodine atom is removed from the perfluoroalkylphosphonate esters by a reducing agent, and replaced by a hydrogen atom.The preferred reducing agent is zinc metal and hydrochloric acid.Typical reduced phosphonate esters are represented by a monomer of theformula and a telomer of the formula The conversion of the reducedphosphonate esters to the phosphonic acids is carried out by hydrolysisin the presence of a mineral acid. The preferred acid is hydrochloricacid. The conversion of the phosphonic acids to the phosphonicdichloride is carried out by heating with PCL, in a suitable solvent.The preferred solvent is carbon tetrachloride.

The conversion of the phosphonic dichloride to the diaziridinylderivative is carried out by reaction with aziridine in a suitableorganic solvent in the presence of an acid acceptor. A variety ofsolvents are suitable and include benzene and chlorinated solvents suchas carbon tetrachloride or methylene chloride. Suitable acid acceptorsinclude tertiary organic bases such as triethylamine and inorganic basessuch as sodium or potassium hydroxide. The preferred base istriethylamine. Typical diaziridinyl derivatives are represented by amonomer of the formula and a telomer of the formula Each of the new typeperfluoroalkyl phosphonic compounds mentioned above is useful as aprecursor to the type compound which follows. Finally, the aziridinylderivatives are useful as oil and water repellents for textiles,particularly for cotton or other cellulosic textiles, and for paper. Thephosphonic acid derivatives have use as potential foaming agents.

The perfluoroalkyl aziridinyl phosphine oxide can be applied tocellulosic materials from a variety of solvents. Suitable solvents arewater, alcohols such as ethanol or methanol and glycol ethers such asethylene glycol monoethyl ether. The preferred solvent is water. Thepreferred concentration of the phosphine oxides used in the solutionsdepends on the particular phosphine oxide being used and on the degreeof oil and water repellency desired, and may vary about from 3% to byweight of the total solution. Aqueous solutions are preferred.

Polymerization of the phosphine oxides on the cellulosic material iscarried out in the presence of latent acid catalysts such as magnesiumchloride, zinc nitrate, or zinc fluoborate. The catalyst concentrationmay vary about from 0.5% to 2% by weight of the total solution, thepreferred concentration depending on the concentration of the phosphineoxide.

The polymerization on cellulosic materials may be carried out byimpregnating the cellulosic material with a solution of the phosphineoxide and catalyst, drying, and curing at temperatures ranging aboutfrom 120C. to 160C. for periods of time about from 3 minutes to 30minutes, the longer times being used with the lower temperatures.

Cotton fabrics which have been treated by the processes of thisinvention are tested for oil repellency, water repellency, and drycleaning durability by AATCC Standard Method No. ll8-1966T, 22-1964, and86-1963T, respectively. These tests are recommended by the AmericanAssociation of Textile Chemists and Colorists. Laundering durabilitytests on the cotton fabrics are performed in an automatic home typewashing machine using a detergent, followed by a 50 minute drying cyclein a tumble dryer. Screening laundry tests were carried out in aTergitometer using a detergent.

The following examples illustrate procedures that have been successfullyused in carrying out the invention and are not meant as a limitationthereof.

PREPARATION OF PERFLUOROALKYLPHOSPHONIC COMPOUNDS EXAMPLE I Diethyll-iodo-lH, 2H, 2H-perfluorononylphosphonate (la) and tetraethyl 1-( 1H,

1 H-perfluorooctyl )-3-iodo-1 ,3-trimethylenediphosphonate (lb)Diethylvinylphosphonate (57.8g., 0.35 mole) and perfluoroheptyl iodide(192.1 g, 0.39 mole) were placed into a 3-neck rb flask equipped with amagnetic stirrer, thermometer, gas inlet tube, and condenser connectedto a mercury air trap. Light was excluded by covering the flask withaluminum foil. Azobis- (isobutyronitrile) catalyst (1.15 g, 0.007 mole)was added and the system flushed with nitrogen. The flask was heated ina water bath to at which temperature an exothermic reaction began. Anice bath was used to keep the temperature below 150C. Reactiontemperature was then maintained at approximately for 6 hours. Unreactedmaterial g) was removed by vacuum distillation below 50C (0.3 mm). Theresidue (153.1 g) was crude mixed iodo-esters (l). A small amount of lwas distilled under vacuu. The iodo-adduct (la) had bp 1081 14C (0.03mm), D 1.3930.

Anal. Calcd. for C H F lO P: C, 23.65; H, 1.99; F, 43.17; 1, 19.22; P,4.69; mol. wt., 660. Found: C, 23.81; H, 2.02; F, 43.17; 1, 19.09; P,4.90; mol. wt. (benzene), 650.

The iodo-telorner (1b) had bp l44-146C (0.03 mm); n 'D 1.4074.

Anal. Calcd. for C,,,H ,F,,IO,,P C, 27.69; H, 3.18; F, 34.57; 1, 15.40;P, 7.52; mol. wt., 824. Found: C, 27.80; H, 3.14; F, 34.55; 1, 15.18; P,7.24; mol. wt. (benzene), 830.

EXAMPLE 2 Diethyl 1H, 1H, 2H, ZH-perfluorononylphosphonate (11a) andtetraethyl 1-( 1H, 1 H-perfluorooctyl )-1 ,3-trimethylenediphosphonate(11b) A slurry of 30 g of zinc dust in 200 ml of ethanol was heated in awater bath to 60C with stirring. An ethanolie solution of] (153. 1 g)and 75 ml of cone. hydrochloric acid were added from separate droppingfunnels within 30 minutes. The bath temperature was raised to 70C then15 g of zinc and 40 ml of hydrochloric acid were added in incrementsover 1 hour. The

mixture was heated an additional hour at 80C, cooled, filtered andconcentrated on a rotary evaporator. The concentrate was washed withdistilled water, then taken up in diethyl ether. The ether solution waswashed with sodium bicarbonate, then with water to neutrality. The ethersolution was dried over sodium sulfate, filtered and concentrated on arotary evaporator. The reduced esters (113 g) were distilled undervacuum to give 40.9 g (22% yield from diethyl vinyl phosphonate (DEVP)of 11a, n D 1.3538; 9.3 g of intermediate fraction, n D 1.3694; 42.3 g(35% yield from DEVP) of 11b, n D 1.3857; and 14.2 g of residue. Theresidue was stirred with absolute ethanol and filtered to give a finebrown solid (unidentified). The filtrate was concentrated to give a darkbrown liquid be lieved to be another telomer, n 3.

Redistillation of a portion of 11a gave bp 8284C. (0.05 mm).

Anal. Calcd. for C, H, F, O P: C, 29.23; H, 2.64; F, 53.35; P, 5.80.Found: C, 29.34; H, 2.84; F, 53.18; P, 5.59. 2

11!; had bp l38-140C. (0.05 mm).

Anal. Calcd for C H F O P C, 32.68; H, 3.90; F, 40.81; P, 8.87; mol.wt., 698. Found: C, 32.73; H, 4.00; F, 40.88; P. 8.69; mol. wt.(chloroform), 702.

Anal. Solid residue; C, 28.79; H, 3.36; F, 29.35; P, 10.34.

Anal. Liquid residue: Calcd for C H F O P C, 34.82; H, 4.67; F, 33.04;P, 10.77. Found: C, 33.37; H,

EXAMPLE 3 1H, 1H, 2H, 2H-perfluorononylphosphonic dichloride (Illa) Ila(40 g, 0.075 mole) was heated with 100 ml of conc. hydrochloric acid atgentle reflux for 3 hours. The mixture was concentrated under vacuum toa gelatinous mass. Conc. hydrochloric acid (75 ml) was added to themixture and refluxed overnight. The mixture was again concentrated undervacuum. Benzene was added and the remaining water removed by azeo tropicdistillation into a Dean-Stark trap. After removal of benzene, the solidresidue was dried under vacuum at 105C to a constant weight to give thecrude acidadduct. This crude acid was dispersed in carbon tetrachlorideand added to a rb flask equipped with a magnetic stirrer, condenser anddrying tube. The mixture was heated to gentle reflux then phosphoruspentachloride (36.6 g, 0.176 mole) was added cautiously in smallportions through the condenser. The addition was completed in 30minutes, and the solution refluxed overnight. Sulfur dioxide was bubbledthrough the warm solution to remove excess phosphorus pentachloride. Thesolution was concentrated under water aspirator vacuum, and the residuedistilled at 6972C. (0.04 mm) to give an 83% yield (32.2 g, 0.062 mole)of 111a, a white solid.

Anal. Calcd for C H CI F OP: C, 20.99; H, 0.78; C], 13.77; F, 55.34; P,6.01. Found: C, 20.79; H, 0.89; Cl, 13.76; F, 55.13; P, 5.99.

EXAMPLE 4 1-( 1H, lH-perfluorooctyl 1 ,3-trimethylenediphosphonictetrachloride (lllb) Ilb (57.8 g. 0.083 mole) was heated at gentlereflux for 6 hours with conc. hydrochloric acid (300 ml) in a one literrb flask equipped with a 500 ml defoamerbulb and a condenser. Themixture was cooled in the refrigerator and the liquid decanted from thesolid. More hydrochloric acid was added and the prodedure repeated. Thege1-like material was concentrated in a large evaporating dish on thesteam cone using benzene to remove residual water. The solid residue wasdried under vacuum at 105C to a constant weight to give the crudeacid-telomer, which was then reacted with phosphorus pentachloride asdescribed for the crude acidadduct above. IIIb was distilled at 1256(0.01 mm) to give a 40% yield (21.7 g. 0.033 mole) of a slightly yellowsolid.

Anal. Calcd for C H-,Cl F, O P C, 20.02; H, 1.07; Cl, 21.49; F, 43.18;P, 9.39; mol. wt., 660. Found: C, 20.16; H, 1.14; Cl, 21.54; F, 43.29;P, 9.21; mol. wt. (chloroform), 673.

EXAMPLE 5 1 H, 1 H,2H,2H-perfluorononylphosphonic acid (IVa) Illa (2 g.0.004 mole) was dissolved in chloroform, then heated with 10 g of waterin an evaporating dish. Residual water was removed by heating withbenzene to dryness. The waxy solid residue was dried in a vacuum oven at105C. to a constant weight to give a 97% yield of IVa, mp l558.

Anal. Calcd for C H F O P: C, 22.61; H, 1.27; F, 59.61; P, 6.48; mol.wt., 478. Found: C, 22.33; H, 1.26; F, 59.73; P, 6.44; mol. wt.(methanol), 471.

EXAMPLE 6 l-( l H, l H-perfluorooctyl l ,3-trimethylenediphosphonic acid(IVb) IVb was prepared from "1b as described for [Va except it was driedto constant weight in a vacuum desiccator at room temperature.

Anal. Calcd for C H F O P C, 22.54, H, 1.89; F, 48.62; P, 10.57. Found:C, 22.75; H, 1.95; F, 48.68; P, 10.77.

EXAMPLE 7 l H, l H,2H,2H-perfluorononylbis( l-aziridinyl) phosphineoxide (Va) Redistilled triethylamine (12.6 g, 0.124 mole) andredistilled aziridine (5.4 g, 0.124 mole) in carbon tetrachloride 100ml) was added to a 4-neck rb flask equipped with a mechanical stirrer,thermometer, dropping funnel and condenser with drying tube. The flaskwas cooled to 5 in an ice bath. "la (29 g, 0.056 mole) in ml of carbontetrachloride was added from the dropping funnel at such a rate as tokeep the reaction temperature below 10. After the addition, the reactiontemperature was allowed to rise to room temperature. The reactionmixture was heated at 3540with stirring for 1 hour. The copious whiteprecipitate was removed by vaccum filtration, rinsed thoroughly withcarbon tetrachloride and dried to give 14.7 g yield) of triethylaminehydrochloride. The filtrate was cooled at 0 overnight then filtered bygravity through sodium sulfate. The clear filtrate was concentrated toapproximately ml on a rotary evaporator below 40. The solution wastreated with decolorizing carbon and sodium sulfate then filtered byvacuum through diatomaceous earth. The filtrate was again concentratedto approximately 75 ml then m1 of petroleum ether (3060) was added. Thesolution was stored at -20 for 1 hour. The liquid was decanted throughfilter paper (filtrate No. 1). The slurry of white precipitate wasredissolved in 100 ml of petroleum ether and stored at 20C. overnight.The white waxy precipitate was filtered by vacuum, washed thoroughlywith cold petroleum ether and dried in a desiccator to give 8.9 g of Va,mp 4950; average aziridinyl assay of duplicate samples, 99.7%. Theconcentrated filtrate was diluted with petroleum ether and a second cropof crystals 10.1 g) was obtained; mp 4244C, average aziridinyl assay ofduplicate samples, 97.7%. The filtrate was combined with filtrate No. land concentrated to a yellow solid residue (7.1 g). The first and secondcrop of crystals gave a 64% yield of Va.

Anal. Calcd for C ,H, F N OP: C, 29.59; H, 2.29; F, 53.95; N, 5.30; P,5.86; mol. wt., 528. Found: C, 29.50; H, 2.41; F, 54.00; N, 5.33; P,5.78; mol. wt. (methanol), 530.

EXAMPLE 8 1-( l H, l H-perfluorooctyl)- 1 ,3-trimethylenebis[di(aziridny1) phosphine oxide] (Vb) Vb was prepared from lVb asdescribed for Va to give a 64% yield; mp 103l07C; aziridinyl assay97.3%. (Vb was obtained as a slightly purer product when dissolved incarbon tetrachloride and a polymeric material removed by filtration;aziridinyl assay, 100.2%).

Anal. Calcd for C H F N O P C, 33.25; H, 3.38; F, 41.52; N, 8.16; P,9.03; mol. wt., 686. Found: C, 33.07; H, 3.14; F, 41.42; N, 8.08; P,9.15; mol. wt. (chloroform), 691.

APPLICATION TO COTTON FABRIC In all of the following examples cottonprintcloth was used. In some cases the cloth contained the wash-wearfinish, dimethylol ethylene urea. The printcloth was immersed in thesolution and the excess squeezed out by passing through squeeze rolls toa wet pickup of 8085%. The fabric was then dried and cured in a forceddraft oven, and finally rinsed and dried.

The two compounds used in the following examples are 1H,1H,2H,2H-perfluorononylbis( 1- aziridinyl )phosphine oxide and l-(1H,1H- perfluorooctyl 1 ,3-trimethylenc-bis[di( 1 aziridinyl phosphineoxide. For brevity the two compounds will be designated FNAP andtelomer, respectively. The term oil rating will be abbreviated OR."

EXAMPLE 9 A solution was prepared by dissolving FNAPO (0.5 grams) in acombination of water (4.5 grams) and ethanol (5.0 grams). The solutioncontained 5% FNAPO by weight. A sample of printcloth was immersed in 1%aqueous zinc fluoborate, the excess aqueezed out, and the fabric dried.The thus impregnated fabric was then impregnated with the FNAPOsolution, dried for 30 minutes at room temperature and cured for 20minutes.

EXAMPLE 10 Printcloth was treated as in Example 9 except that thesolvent was ethanol instead of water-ethanol and the fabric was curedfor 5 minutes at 150C. The OR of the fabric was 6. After 5 launderingsthe OR was 2.

EXAb/[PLE l l Printcloth was treated as in Example 9 except that thesolvent was ethylene glycol monoethyl ether, and 2% zinc fluoborate wasused, and the fabric was dried for 3 minutes at C. The OR of the fabricwas 6. After 5 launderings the OR was 3.

EXAMPLE 12 A 5% aqueous solution of FNAPO containing 1% zinc fluoboratewas prepared and applied to cotton printcloth from a single bath. Thecloth was dried for 5 minutes at C and cured for 5 minutes at C. Thestrength retention of the fabric was good. The weight gain of the fabricwas 2.1% and the OR was 6. After 5 launderings the OR was 3 and after 5dryeleanings the OR was 2. The spray rating was 50 both before and after5 launderings.

Printcloth was treated in the same manner except that a 3% aqueoussolution of FNAPO containing 0.6% zinc fluoborate was used. Similarresults on oil and water repellency and strength retention wereobtained.

EXAMPLE 13 The two treatments in Example 12 were repeated except thatthe fabric used was treated with dimethylol ethyleneurea to impartwash-wear properties prior to treatment with FNAPO. Similar results onoil and water repellency were obtained. Fabric strength was lower due tothe wash-wear finish.

EXAMPLE 14 Cotton printcloth was impregnated with an aqueous solutioncontaining 5% FNAPO and 0.5% zinc fluoborate. The fabric was dried for 5minutes at 85C and cured for 5 minutes at C. The OR was 6. After 5launderings in a Tergitometer the OR was 2, and after a 3 hourextraction in a Soxhlet extractor the OR was EXAMPLE 15 Two printclothsamples were treated as in Example 14 except 1% zinc fluoborate was usedand one sample was cured for 3 minutes at C, and the other cured for 10minutes at 160C. The first sample had an OR of 5. After 5 launderings ina Tergitometer the OR was 3. The second sample had an original OR of 6,and an OR of 3 after 5 launderings in a Tergitometer. The OR of thesamples was unaffected by extraction with tetrachloroethylene.

EXAMPLE 16 Cotton printcloth was impregnated with an aqueous solutioncontaining 10% FNAPO and 1% zinc fluoborate. The fabric was dried for 5minutes at 85C and cured for 5 minutes at 160C. The OR was 6 before andafter extraction with tetrachloroethylene and 4 after five Tergitometerlaunderings.

EXAMPLE 1 7 Printcloth was treated as in Example 16 except a 5% solutionof FNAPO was used and the fabric was cured for 30 minutes at 120Cwithout predrying. The OR was 6 before and after tetrachloroethyleneextraction.

EXAMPLE 1:;

before and after 5 home launderings or 5 drycleanings. The OR was 2after 3 hours extraction with tetrachloroethylene in a Soxhletextractor.

We claim:

1. l-( "-1, l H-perfluoroiictyl l ,3-trimethylenebin[- di(l-aziridinyl)phosphine oxide] substantially free of 1H, 1H, 2H,2H-perflu0rononylbis(l-aziridinyl)phosphine oxide.

1. 1-(LH, LH-PERFLUOROCTYL)-1,3-TRIMETHYLENEBIN(DI(1AZARIDINARYL)PHOSPHINE OXIDE) SUBSTANTIALLY FREE OF 1H, 1H, 2H,2H-PERFOUORONONYLBIST(1-ARIDINARYLE PHOSPHINE OXIDE.